CN103547774A - Exhaust gas purification device - Google Patents

Exhaust gas purification device Download PDF

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Publication number
CN103547774A
CN103547774A CN201280011011.9A CN201280011011A CN103547774A CN 103547774 A CN103547774 A CN 103547774A CN 201280011011 A CN201280011011 A CN 201280011011A CN 103547774 A CN103547774 A CN 103547774A
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CN
China
Prior art keywords
ozone
waste gas
fluid
oxygen
selective reduction
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Granted
Application number
CN201280011011.9A
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Chinese (zh)
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CN103547774B (en
Inventor
细谷满
川田吉弘
佐藤信也
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Hino Motors Ltd
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Hino Motors Ltd
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Publication date
Priority claimed from JP2011056111A external-priority patent/JP2012193620A/en
Priority claimed from JP2011143032A external-priority patent/JP5952533B2/en
Application filed by Hino Motors Ltd filed Critical Hino Motors Ltd
Publication of CN103547774A publication Critical patent/CN103547774A/en
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Publication of CN103547774B publication Critical patent/CN103547774B/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9431—Processes characterised by a specific device
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/10—Preparation of ozone
    • C01B13/11—Preparation of ozone by electric discharge
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
    • F01N3/106—Auxiliary oxidation catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/104—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2201/00—Preparation of ozone by electrical discharge
    • C01B2201/60—Feed streams for electrical dischargers
    • C01B2201/64—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2201/00—Preparation of ozone by electrical discharge
    • C01B2201/60—Feed streams for electrical dischargers
    • C01B2201/66—Pretreatment of the feed
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/38—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an ozone (O3) generator, e.g. for adding ozone after generation of ozone from air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/06—Adding substances to exhaust gases the substance being in the gaseous form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

A selective reduction-type catalyst (19) capable of reducing the NOx in exhaust gas to N2 is disposed in an exhaust pipe (16) of an engine (11). A fluid feed means (21) has a fluid spray nozzle (23) facing the exhaust tube on the exhaust gas upstream side from the selective reduction-type catalyst. The fluid feed means is configured such that a urea fluid (22) that functions as a reducing agent is fed with the selective reduction-type catalyst from the fluid spray nozzle to the exhaust pipe. Ozone feed means (41) comprises an ozone spray nozzle (43) that faces the exhaust pipe on the exhaust gas upstream side that is the exhaust gas upstream side from the selective reduction-type catalyst, or the exhaust gas downstream side from the fluid spray nozzle. The ozone feed means is configured such that ozone (42), which is capable of oxidizing the No contained in the exhaust gas to NO2, is fed from the ozone spray nozzle to the exhaust pipe. The NOx are reduced, even when the exhaust gas temperature is low, and as a result, the Nox can be efficiently reduced within a broad exhaust gas temperature range from low temperature to high temperature.

Description

Waste gas cleaning plant
Technical field
The present invention relates to the waste gas (Japanese: row's mood ガ ス) contained oxynitrides is (hereinafter referred to as NO for reducing diesel engine xthereby) device of purifying exhaust air.
Background technique
In the past, as this waste gas cleaning plant, disclose the waste gas cleaning plant of such internal-combustion engine, disposes NO on the exhaust passageway of internal-combustion engine that is: xholder; Than NO xin the exhaust passageway of the more top trip of holder, dispose for import the ozone of ozone to exhaust passageway and import parts; Than NO xin the exhaust passageway that holder is swum more on the lower, dispose 3 yuan of catalyzer; In the upstream of 3 yuan of catalyzer, dispose selective reduction type catalyzer, this selective reduction type catalyzer is modulated at than the low temperature of these 3 yuan of catalyzer and manifests activity; In the upstream of selective reduction type catalyzer, also dispose oxygen and import parts, the waste gas that these oxygen importing parts are used for oxygen to import to the upstream of selective reduction type catalyzer is (for example,, with reference to patent documentation 1.）。
In the waste gas cleaning plant of the internal-combustion engine forming like this, because selective reduction type catalyzer is to modulate in the mode of activate at the temperature lower than 3 yuan of catalyzer, so there is the NO of making xwith HC(hydrocarbon) effect reacting, purify under oil-poor atmosphere.Consequently, can, before 3 yuan of catalyst activities, could not contain or be adsorbed on NO xnO in holder xeffectively purify, can improve NO xpurifying property.In addition, due to the cause of selective reduction type catalyst arrangement in the upstream of 3 yuan of catalyzer, so when the cold start-up of internal-combustion engine, can make selective reduction type catalyzer manifest rapidly activity, after the activity of 3 yuan of catalyzer manifests to a certain extent, the NO that the enough 3 yuan of catalyzer of energy purge selected reduction catalyst xcarry out purified treatment.Consequently, can improve NO xpurifying property.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-163881 communique (claim 1, " 0014 " section, " 0015 " section, Fig. 8)
Summary of the invention
, in the waste gas cleaning plant of the internal-combustion engine shown in above-mentioned patent documentation 1 in the past, owing to being by HC(hydrocarbon in selective reduction type catalyzer) by NO xthe cause purifying, so NO when exhaust gas temperature is low xminimizing efficiency still lower.
The 1st object of the present invention, is to provide and a kind ofly when exhaust gas temperature is low, also can effectively reduces NO xwaste gas cleaning plant.The 2nd object of the present invention, is to provide and a kind ofly can substantially in whole exhaust gas temperature region, can effectively reducing NO xwaste gas cleaning plant.
The 1st viewpoint of the present invention is a kind of waste gas cleaning plant, as shown in Figure 1, this waste gas cleaning plant has: and selective reduction type catalyzer (Japanese: catalyst) 19, this selective reduction type catalyzer 19 is arranged in the outlet pipe 16 of motor 11, and it can be by the NO in waste gas xbe reduced into N 2; Fluid supply part 21, this fluid supply part 21 has fluid tip 23, this fluid tip 23 is facing to more leaning on the outlet pipe 16 of waste gas upstream side than selective reduction type catalyzer 19, this fluid supply part 21 is for Urea Series fluid 22 is supplied to outlet pipe 16 from fluid tip 23, and this Urea Series fluid 22 plays a role as reducing agent in selective reduction type catalyzer 19; With ozone supply parts 41, these ozone supply parts 41 have ozone nozzle 43, this ozone nozzle 43 is facing to more more leaning on the outlet pipe 16 of waste gas upstream side or exhaust gas downstream side by waste gas upstream side and than fluid tip 23 than selective reduction type catalyzer 19, these ozone supply parts 41 are for ozone 42 is supplied to outlet pipe 16 from ozone nozzle 43, and this ozone 42 can be oxidized to NO by the NO in waste gas 2.
The 2nd viewpoint of the present invention is the invention based on the 1st viewpoint, and as shown in Figure 2, it is characterized in that, it also has: ozone generating-device 70 and oxidation catalyst 92, the airborne oxygen generation of this ozone generating-device 70 use ozone 42; This oxidation catalyst 92 is arranged on than fluid tip 23 and ozone nozzle 42 and more leans in the outlet pipe 16 of waste gas upstream side, and it can be oxidized to NO by the NO in waste gas in the exhaust gas temperature that is more than or equal to regulation 2.
The 3rd viewpoint of the present invention is the invention based on the 2nd viewpoint, and as shown in Figures 3 and 4, it is characterized in that, ozone generating-device 70 has: compressor 71, and this compressor 71 is for by air compressing; Exsiccator 72, this exsiccator 72 is for making by the Compressed air drying after 71 compressions of this compressor; Ozonizer 73, this ozonizer 73 is for changing into ozone a part for the oxygen by these exsiccator 72 dried pressurized air; With air separator 74, this air separator 74 is arranged between exsiccator 72 and ozonizer 73, it is for be separated into the nitrogen-rich gas that oxygen-rich gas that oxygen concentration is high and nitrogen gas concn are high by the dried pressurized air of exsiccator 72, this ozone generating-device 70 is constituted as, a part for oxygen in oxygen-rich gas by after air separator 74 separation is imported in ozonizer 73, by ozonizer 73, convert it into ozone, by the nitrogen-rich gas by after air separator 74 separation, the moisture in exsiccator 72 is removed and made exsiccator 72 regeneration.
The 4th viewpoint of the present invention is the invention based on the 3rd viewpoint, and as shown in Fig. 3, Fig. 4 and Fig. 7, it is characterized in that, air separator 74 consists of oxygen permeable membrane 74a, oxygen-rich gas sees through oxygen permeable membrane 74a by the dried pressurized air of device 72 that makes to be dried and generates, nitrogen-rich gas by make to be dried the dried pressurized air of device 72 only through and do not see through oxygen permeable membrane 74a and generate.
The 5th viewpoint of the present invention is based on the 3rd or the invention of the 4th viewpoint, and as shown in Figures 3 and 4, it is characterized in that, it is constituted as, by the nitrogen-rich gas after air separator 74 separation, through after scavenge pipe 76, be fed into exsiccator 72, in scavenge pipe 76, be provided with nitrogen-rich gas flow rate regulating valve 79, this nitrogen-rich gas flow rate regulating valve 79 is for adjusting the flow through the nitrogen-rich gas of scavenge pipe 76.
The 6th viewpoint of the present invention is the invention based on any one viewpoint in the 3rd to the 5th viewpoint, and as shown in Figures 3 and 4, it is characterized in that, between compressor 71 and exsiccator 72, be provided with gas tank 78, this gas tank 78 is for storing by the pressurized air after compressor 71 compressions.
The 7th viewpoint of the present invention is based on the 1st or the invention of the 2nd viewpoint, and as shown in Figure 1 or 2, it is characterized in that, Urea Series fluid 22 is any one in ammonia or aqueous solution of urea.
The 8th viewpoint of the present invention is based on the 1st or the invention of the 2nd viewpoint, and as shown in Figure 1 or 2, it is characterized in that, selective reduction type catalyzer 19 on honeycomb substrate, applies zeolite or zirconium oxide forms.
The 9th viewpoint of the present invention is the invention based on the 2nd viewpoint, and as shown in Figure 2, it is characterized in that, than fluid tip 23 and ozone nozzle 43, more by waste gas upstream side and than oxidation catalyst 92, more by the outlet pipe 16 of exhaust gas downstream side, be provided with particulate filter 93, this particulate filter 93 is for catching the fine particle of waste gas.
The effect of invention
In the waste gas cleaning plant of the 1st viewpoint of the present invention, when ozone is supplied to outlet pipe from the ozone nozzle of ozone supply parts, the NO in waste gas xin NO become rapidly reactive high NO with ozone reaction 2, at the high NO of this reactivity 2after flowing into selective reduction type catalyzer together with Urea Series fluid that fluid tip from fluid supply part is supplied to outlet pipe, even when exhaust gas temperature is low, reactive high NO 2also can in selective reduction type catalyzer, carry out selective reduction and be reduced into N with Urea Series fluid 2.Consequently, when exhaust gas temperature is low, also can effectively reduce NO x.
In the waste gas cleaning plant of the 2nd viewpoint of the present invention, when ozone is supplied to outlet pipe from the ozone nozzle of ozone supply parts, the NO in waste gas xin NO become rapidly reactive high NO with ozone reaction 2, at the high NO of this reactivity 2after flowing into selective reduction type catalyzer together with Urea Series fluid that fluid tip from fluid supply part is fed into outlet pipe, even when exhaust gas temperature is low, reactive high NO 2also can in selective reduction type catalyzer, carry out selective reduction and be reduced into N with Urea Series fluid 2.Consequently, when exhaust gas temperature is low, also can effectively reduce NO x.On the other hand, owing to becoming in exhaust gas temperature after the temperature that is more than or equal to regulation, oxidation catalyst is just oxidized to the NO in waste gas reactive high NO 2so, at the high NO of this reactivity 2after flowing in selective reduction type catalyzer together with being fed into the Urea Series fluid outlet pipe with fluid tip from fluid supply part, even if exhaust gas temperature uprises, reactive high NO 2also can in selective reduction type catalyzer, carry out selective reduction and be reduced into N with Urea Series fluid 2.Consequently, even if exhaust gas temperature uprises, also can effectively reduce NO x.Therefore, almost in whole exhaust gas temperature region, can effectively reduce NO x.
In the waste gas cleaning plant of the 3rd viewpoint of the present invention, because handle is imported in ozonizer by a part for the oxygen in the oxygen-rich gas after air separator separation, by ozonizer, convert it into ozone, by the nitrogen-rich gas by after air separator separation, the moisture in exsiccator is removed and exsiccator is regenerated, so can effectively make exsiccator regeneration.That is, owing to can the air by after compressor compresses not being directly used in to the purposes that makes exsiccator regeneration, so can suppress the consumption figure by the air after compressor compresses.Consequently, owing to can reducing the capacity that spues of compressor, so can seek the miniaturization of compressor.In addition, if oxygen-rich gas is increased, the amount of moisture in the pressurized air that the device that is dried is removed also increases, however, but owing to also being increased by the nitrogen-rich gas of air separator separation, so this can utilize the nitrogen-rich gas of this increase to remove the moisture increasing in exsiccator.Consequently, even oxygen-rich gas increase and decrease, nitrogen-rich gas also increases and decreases with this increase and decrease, therefore can effectively make exsiccator regeneration.
In the waste gas cleaning plant of the 4th viewpoint of the present invention, owing to utilizing oxygen permeable membrane to form air separator, by the dried pressurized air of device that makes to be dried, see through oxygen permeable membrane and generate oxygen-rich gas, by make to be dried the dried pressurized air of device only through and do not see through oxygen permeable membrane and generate nitrogen-rich gas, so, even if there is hydrocarbon, no matter this hydrocarbon adheres to or is non-cohesive on oxygen permeable membrane, can be by oxygen permeable membrane, oxygen-rich gas and nitrogen-rich gas is separated reliably.Consequently, no matter whether hydrocarbon is attached on oxygen permeable membrane, and the oxygen-rich gas being undertaken by oxygen permeable membrane and the separating property of nitrogen-rich gas can not reduce.
In the waste gas cleaning plant of the 5th viewpoint of the present invention, in be supplied to the scavenge pipe of exsiccator by the nitrogen-rich gas after air separator separation, be provided with flow rate regulating valve.Consequently, compressor is being maintained under the state of specified running, only with flow rate regulating valve adjustment, passing through the flow of the nitrogen-rich gas of scavenge pipe, just can also adjust the flow of oxygen-rich gas.Also have, owing to can not using for adjusting the voltage stabilizer of the compressed-air actuated pressure after being compressed by compressor, and do not use for the compressed-air actuated knock out drum of interim storage, surge tank, so can form ozone generating-device by enough fewer component, and can reduce compressed-air actuated stream impedance, therefore can make the further miniaturization of compressor.
In the waste gas cleaning plant of the 6th viewpoint of the present invention, owing to being provided with between compressor and exsiccator for storing the compressed-air actuated gas tank after being compressed by compressor, even if so the flow of oxygen-rich gas and nitrogen-rich gas is sharply changed, also can in air separator, supply with the pressurized air of sufficient quantity, and can relax compressed-air actuated pressure oscillation.
Accompanying drawing explanation
Fig. 1 is the pie graph of the waste gas cleaning plant of the present invention's the 1st mode of execution.
Fig. 2 means the pie graph of the waste gas cleaning plant of the present invention's the 2nd mode of execution.
Fig. 3 is the pie graph of the air loop of the ozone generating-device that uses of the waste gas cleaning plant of the 2nd mode of execution.
Fig. 4 means A-A line sectional view ozone generating-device, Fig. 5 of the 2nd mode of execution.
Fig. 5 means B-B line sectional view ozone generating-device, Fig. 4 of the 2nd mode of execution.
Fig. 6 be form hollow line that the water vapour diffusion barrier of the exsiccator of this ozone generating-device uses want portion's amplification profile diagram.
Fig. 7 be form hollow line that the oxygen permeable membrane of air separator uses want portion's amplification profile diagram.
Fig. 8 means the NO when having used Urea Series fluid for aqueous solution of urea and having changed the waste gas cleaning plant of embodiment 1, embodiment 2 and comparative example 1 of the adding quantity of ozone xthe figure that slip changes with the variation of exhaust gas temperature.
Fig. 9 means the NO when having used Urea Series fluid for ammonia and having changed the waste gas cleaning plant of embodiment 3, embodiment 4 and comparative example 2 of the adding quantity of ozone xthe figure that slip changes with the variation of exhaust gas temperature.
Figure 10 means the NO when having used Urea Series fluid for aqueous solution of urea and having changed the waste gas cleaning plant of embodiment 5, embodiment 6 and comparative example 3 of the adding quantity of ozone xthe figure that slip changes with the variation of exhaust gas temperature.
Figure 11 means the NO when having used Urea Series fluid for ammonia and having changed the waste gas cleaning plant of embodiment 7, embodiment 8 and comparative example 4 of the adding quantity of ozone xthe figure that slip changes with the variation of exhaust gas temperature.
Embodiment
Based on accompanying drawing, explanation is used for implementing mode of the present invention below.
(the 1st mode of execution)
As shown in Figure 1, on the suction port of diesel engine 11, by intake manifold 12, be connected with suction tude 13, on relief opening, by gas exhaust manifold 14, connect by outlet pipe 16.In suction tude 13, be respectively arranged with the compression case 17a of turbocharger 17 and to carried out the interstage cooler 18 of cooling use by the air inlet after turbocharger 17 compressions, on outlet pipe 16, be provided with the turbosupercharging casing 17b of turbocharger 17.In compression case 17a, rotatably contain compressor rotor (not shown), in turbosupercharging casing 17b, rotatably contain turbo machine rotor (not shown).Compressor rotor and turbo machine rotor are linked by transmission shaft (not shown), it is configured to, the energy of the waste gas that compressor rotor is discharged from motor 11 by turbo machine rotor and transmission shaft utilization is rotated, and the air amount in suction tude 13 can utilize the rotation of this compressor rotor to compress.
Outlet pipe 16 midway on be provided with selective reduction type catalyzer 19.Selective reduction type catalyzer 19 is housed in diameter than in the large casing 15 of outlet pipe 16.Selective reduction type catalyzer 19 is integral catalyzers, and it on the honeycomb substrate of steinheilite system, applies zeolite or zirconium oxide forms.As zeolite, can enumerate copper zeolite, iron zeolite, zinc zeolite, cobalt zeolite etc.The selective reduction type catalyzer 19 consisting of copper zeolite can apply and contain the paste formation of having carried out the zeolite powder after ion exchange with copper on honeycomb substrate.In addition, the selective reduction type catalyzer 19 consisting of iron zeolite, zinc zeolite or cobalt zeolite can apply and contain the paste formation of having carried out the zeolite powder after ion exchange with iron, zinc or cobalt on honeycomb substrate.Also have, the selective reduction type catalyzer 19 consisting of zirconium oxide can apply and contain the paste formation of having adsorbed zirconic γ-aluminium powder or θ-aluminium powder on honeycomb substrate.
On the other hand, than selective reduction type catalyzer 19, more by the outlet pipe 16 of waste gas upstream side, be provided with fluid supply part 21, this fluid supply part 21 is for being supplied to Urea Series fluid 22 this outlet pipe 16.Fluid supply part 21 has: fluid tip 23, and this fluid tip 23 is facing to more leaning on the outlet pipe 16 of waste gas upstream side than selective reduction type catalyzer 19; Fluid supply line 24, the top of this fluid supply line 24 is connected in fluid tip 23; Tank 26, this tank 26 is connected in the cardinal extremity of this fluid supply line 24, and it is for stores urine prime system fluid 22; Pump 27, this pump 27 for by Urea Series fluid 22 pressurized delivered in this tank 26 to fluid tip 23; Adjust valve 31 with fluid delivery volume, this fluid delivery volume is adjusted valve 31 for adjusting the delivery volume (emitted dose) of the Urea Series fluid 22 ejecting from fluid tip 23.Above-mentioned Urea Series fluid 22 is in selective reduction type catalyzer 19, as reducing agent, to bring into play the ammonia of function or any one in aqueous solution of urea.In addition, said pump 27 is located on the fluid supply line 24 between fluid tip 23 and tank 26, and fluid delivery volume is adjusted valve 31 and is located on the fluid supply line 24 between fluid tip 23 and pump 27.And, fluid delivery volume is adjusted valve 31 and is comprised that hydrodynamic pressure is adjusted valve 32 and open and close valve 33 for fluid, wherein, hydrodynamic pressure is adjusted valve 32 and is located at fluid supply line 24, it is for adjusting the supply pressure of the Urea Series fluid 22 of supplying with to fluid tip 23, fluid is located at the cardinal extremity of fluid tip 23 with open and close valve 33, it is for opening and closing the cardinal extremity of fluid tip 23.
It is the three-way valve with the 1st～3rd mouthful of 32a～32c that hydrodynamic pressure is adjusted valve 32, and the 1st mouthful of 32a is connected in the discharge opening of pump 27, and the 2nd mouthful of 32b is connected in fluid and by reflow pipe 34, is connected in tank 26 with 33, the 3 mouthfuls of 32c of open and close valve.After driving fluid pressure-regulating valve 32, by the Urea Series fluid 22 of pump 27 pressurized delivered, from the 1st mouthful of 32a incoming fluid pressure-regulating valve 32, at hydrodynamic pressure, adjust valve 32 and be adjusted to after the pressure of regulation, from the 2nd mouthful of 32b, be pressed and delivered to open and close valve 33 for fluid.In addition, stop hydrodynamic pressure and adjust after the driving of valve 32, by the Urea Series fluid 22 of pump 27 pressurized delivered, from the 1st mouthful of 32a incoming fluid pressure-regulating valve 32, from the 3rd mouthful of 32c, by reflow pipe 34, turned back to tank 26.
On the other hand, than selective reduction type catalyzer 19, more by the outlet pipe 16 of waste gas upstream side, be provided with ozone supply parts 41, these ozone supply parts 41 are for supplying with and the NO in waste gas can be oxidized to NO to this outlet pipe 16 2ozone 42.Ozone supply parts 41 have: ozone nozzle 43, and this ozone nozzle 43 is facing to more more leaning on the outlet pipe 16 of waste gas upstream side by waste gas upstream side and than fluid tip 23 than selective reduction type catalyzer 19; Ozone supply pipe 44, the top of this ozone supply pipe 44 is connected in ozone nozzle 43, and cardinal extremity is opened in atmosphere; Compressor 46, this compressor 46 is for being delivered to air pressurized ozone supply pipe 44; Ozonizer 47, this ozonizer 47 is for changing into ozone 42 by a part that is contained in this airborne oxygen; Adjust valve 48 with ozone supply amount, this ozone supply amount is adjusted valve 48 for adjusting the delivery volume (emitted dose) of the ozone 42 ejecting from ozone nozzle 43.The discharge opening of above-mentioned compressor 46 is connected in the cardinal extremity of ozone supply pipe 44, and the suction port of compressor 46 is to atmosphere opening.In addition, ozonizer 47, in the present embodiment, use be silent discharge type.Particularly, ozonizer 47 is formed as follows: there is no interval illustrated, that sky is opened regulation, apply in parallel to each other between setting and one or both pair of electrodes all being covered by dielectrics high frequency high voltage and make it that plasma discharge occur, utilize this plasma discharge that the part containing aerial oxygen is changed into ozone 42.And ozone supply amount adjusts the cardinal extremity that valve 48 is located at ozone nozzle 43, it is constituted as and the cardinal extremity of ozone nozzle 43 can be opened and closed.
More leaning on the casing 15 of waste gas upstream side than selective reduction type catalyzer 19, be provided with temperature transducer 51, this temperature transducer 51 is for detection of the temperature that is about to flow into the waste gas in selective reduction type catalyzer 19.And the rotating speed of motor 11 detects by turn-sensitive device 52, the load of motor 11 is detected by load sensor 53.Each of temperature transducer 51, turn-sensitive device 52 and load sensor 53 detects the control inputs that output is connected in controller 54, and the control output of controller 54 is connected to pump 27, hydrodynamic pressure adjustment valve 32, for fluid, open and close valve 33, compressor 46, ozonizer 47 and ozone supply amount are adjusted valve 48.In controller 54, be provided with storage 56.In this storage 56, store in advance hydrodynamic pressure corresponding to exhaust gas temperature with engine speed, engine loading, selective reduction type catalyst inlet adjust the pressure of valve 32, fluid for the having or not of action of the switching number of times in the unit time of open and close valve 33, pump 27, the having or not of the action of switching number of times, compressor 46 and the ozonizer 47 in the unit time of ozone supply amount adjustment valve 48.In this external storage 56, as mapping graph, store respectively according to NO and NO the waste gas variation of engine speed and engine loading, that discharge from motor 11 2the variation of flow.In addition, because the NO the waste gas of discharging from motor is to NO 2the flow-rate ratio cause different according to the kind of motor, so the above-mentioned mapping graph of every kind of motor all can be changed.
Action to the waste gas cleaning plant of such formation describes.After motor 11 has just started and during motor 11 light running, exhaust gas temperature is lower, is 100～200 ℃.Temperature transducer 51 detects the exhaust gas temperature of this temperature range, turn-sensitive device 52 and load sensor 53 detect after the no-load running or light running of motor 11, controller 54 each detection output based on temperature transducer 51, turn-sensitive device 52 and load sensor 53, drive compression machine 46, ozonizer 47 and ozone supply amount are adjusted valve 48, and driven pump 27, hydrodynamic pressure are adjusted valve 32 and open and close valve 33 for fluid respectively simultaneously.Due to compressor 46 driven after, air is fed in ozonizer 47, ozonizer 47 utilizes plasma discharge to change into ozone 42 containing the part of aerial oxygen.This ozone 42 by the switching of the cardinal extremity of the ozone nozzle 43 being adjusted valve 48 by ozone supply amount and carry out from ozone nozzle 43 off and on injected (supply) to outlet pipe 16.
Here,, to ozone supply 42 in outlet pipe 16, be why for a part of the NO in waste gas being changed into reactive high NO 2, make to be directed to NO in the waste gas in selective reduction type catalyzer 19 to NO 2flow-rate ratio, approach the NO and the NO that by Urea Series fluid 22, are undertaken in selective reduction type catalyzer 19 2to N 2the reduction reaction ratio 1 to 1 of carrying out the most fast.So the mapping graph of controller 54 based on being stored in storage 56, obtains NO the waste gas of discharging from motor 11 to NO 2flow-rate ratio so that be directed to NO in selective reduction type catalyzer 19 to NO 2flow-rate ratio approach 1 to 1 mode, set above-mentioned ozone 42 to the supply flow of outlet pipe 16.After above-mentioned ozone 42 is fed in outlet pipe 16, shown in (1), a part of the NO in waste gas is just by ozone (O 3) 42 promptly change into NO 2.
O 3+NO→O 2+NO 2 ……（1）
On the other hand, driven pump 27, driving fluid pressure-regulating valve 32, opens and closes fluid with after open and close valve 33, Urea Series fluid 22 by fluid supply line 24 off and on injected (supply) in outlet pipe 16.Here, why in outlet pipe 16, supplying with Urea Series fluid 22, is in order to make it as by the NO in waste gas x(NO and NO 2) be reduced into N 2reducing agent play a role.The NO and the NO that have contained the waste gas of discharging from motor 11 2, the NO in ozone 42 these waste gas part oxidation after NO 2, after Urea Series fluid 22 imports in selective reduction type catalyzer 19, even if exhaust gas temperature lower is 100～200 ℃, reactive high NO 2in selective reduction type catalyzer 19, carry out selective reduction and be reduced into N with Urea Series fluid 22 2.When consequently, exhaust gas temperature is low, also can effectively reduce NO x.
Concrete chemical reaction in selective reduction type catalyzer 19, the occasion that is aqueous solution of urea at Urea Series fluid 22, represents that by following formula (2) and formula (3) occasion that is ammonia at Urea Series fluid 22 represents with following formula (4).
（NH 2） 2CO+H 2O→2NH 3+CO 2 ……（2）
NO+NO 2+2NH 3→2N 2+3H 2O ……（3）
NO+NO 2+2NH 3→2N 2+3H 2O ……（4）
Above-mentioned formula (2), represents because exhaust gas temperature is the lower cause of 100～200 ℃, although be fewer amount, is also carrying out aqueous solution of urea (Urea Series fluid 22) to the chemical equation of ammonia hydrolysis.In addition, above-mentioned formula (3), represents NO and NO in waste gas 2in selective reduction type catalyzer 19 with above-mentioned ammonia gas react from aqueous solution of urea hydrolysis, NO and NO 2be reduced into N 2chemical equation.And above-mentioned formula (4), represents NO and NO in waste gas 2in selective reduction type catalyzer 19, react NO and NO with ammonia (Urea Series fluid 22) 2be reduced into N 2chemical equation.Here, because use ammonia as Urea Series fluid 22, than using aqueous solution of urea, can make NO and NO 2to N 2reduction reaction carry out rapidly, so use ammonia comparatively desirable as Urea Series fluid 22.As Urea Series fluid 22, using the occasion of aqueous solution of urea, because aqueous solution of urea is heated to and makes while being more than or equal to 200 ℃ it resolve into after ammonia to be supplied in outlet pipe 16 and can to make NO and NO 2to N 2reduction reaction can promptly carry out, so comparatively desirable.
In addition,, after exhaust gas temperature surpasses 200 ℃, the i.e. detection based on temperature transducer 51 of controller 54 output, stops the driving that compressor 46, ozonizer 47 and ozone supply amount are adjusted valve 48.This is because exhaust gas temperature becomes after higher high temperature, even the NO in waste gas and NO 2flow-rate ratio approach 1 to 1, the NO in waste gas xalso be to react with Urea Series fluid 22 in selective reduction type catalyzer 19, NO and NO 2be reduced into rapidly N 2.
(the 2nd mode of execution)
Fig. 2～Fig. 7 represents the 2nd mode of execution of the present invention.In Fig. 2, the mark identical with Fig. 1 represents identical component.In the present embodiment, than selective reduction type catalyzer 19, more by being provided with on the outlet pipe 16 of waste gas upstream side in this outlet pipe 16, supplying with and the NO in waste gas can be oxidized to NO 2the ozone supply parts 61 of ozone.Ozone supply parts 61 have ozone nozzle 43 and ozone generating-device 70, wherein, ozone nozzle 43 is facing to more more leaning on the outlet pipe 16 of waste gas upstream side by waste gas upstream side and than fluid tip 23 than selective reduction type catalyzer 19, and ozone generating-device 70 is connected in ozone nozzle 43 by ozone supply pipe 44.Ozone generating-device 70 is constituted as the oxygen generation ozone 42 in available air.
As shown in Fig. 3～Fig. 5, above-mentioned ozone generating-device 70 has: compressor 71, and this compressor 71 is for pressurized air; Exsiccator 72, this exsiccator 72 is for making by the Compressed air drying after 71 compressions of this compressor; With ozonizer 73, this ozonizer 73 is for changing into ozone a part for the oxygen by these exsiccator 72 dried pressurized air.In the present embodiment, compressor 71 is constituted as and can be driven by the storage battery of VDC 24V.In addition, in the present embodiment, although compressor is use VDC 24V battery-driven, the crank-driven of motor for compressor, or also can if the words of hybrid electric vehicle use the storage battery of VDC 200～300V to drive.
Exsiccator 72 is by water vapour diffusion barrier 72a(Fig. 6 that water vapour (moisture) easily sees through and air is difficult to see through) be housed in the outer cover 72d of tubular and form.This water vapour diffusion barrier 72a is formed with through hole 72c by the asymmetric hollow line 72b(central authorities of the aromatic polyimide of for example thickness 100 μ m, external diameter 500 μ m and length 450mm, the hollow line 72b on film thickness direction with asymmetrical density structure) tie up rear formation, it is housed in (Fig. 3～Fig. 5) in outer cover 72d along its longitudinal direction.In addition on the lower surface of outer cover 72d, be formed with for importing the air introducing port 72e by the air after compressor 71 compressions, on the upper surface of outer cover 72d, be formed with for discharging by the dried compressed-air actuated air outlet 72f(Fig. 4 of exsiccator 72).Air introducing port 72e is connected in the lower end of each hollow line 72b of water vapour diffusion barrier 72a, air outlet 72f is connected in the upper end of each hollow line 72b of water vapour diffusion barrier 72a, and air introducing port 72e and air outlet 72f are connected with the through hole 72c of each hollow line 72b thus.And, in the side wall upper part of outer cover 72d, be formed with below the purge gas introducing port 72g for nitrogen-rich gas is imported as purge gas describing, in the lower sidewall of outer cover 72d, be formed with a purge gas exhaust port 72h who discharges together with water vapour (moisture) as the nitrogen-rich gas of purge gas for handle.And it is constituted as, the nitrogen-rich gas importing from purge gas introducing port 72g is discharged from purge gas exhaust port 72h by the outer circumferential face of the hollow line 72b of water vapour diffusion barrier 72a.
Here, the internal diameter of through hole 72c(through hole 72c that the pressurized air that contains water vapour (moisture) flows through each hollow line 72b of water vapour diffusion barrier 72a is formed for example 300 μ m.) time, flowing through water vapour in the pressurized air of through hole 72c, just to take the inner surface side of film that is present in hollow line 72b and the difference of the steam partial pressure of outer surface side be driving force, outer surface side infiltration from the inner surface side of the film of the high hollow line 72b of steam partial pressure towards the film of the low hollow line 72b of steam partial pressure, due to this cause, the water vapour flowing through in the pressurized air of through hole 72c of hollow line 72b reduces, and dried pressurized air is discharged from air outlet 72f.
That in the present embodiment, ozonizer 73 uses is silent discharge type (Fig. 3 and Fig. 4).Particularly, ozonizer 73 is formed as follows: there is no interval illustrated, that sky is opened regulation, apply in parallel to each other between setting and one or both pair of electrodes all being covered by dielectrics high frequency high voltage and make it that plasma discharge occur, utilize this plasma discharge that the part containing aerial oxygen is changed into ozone.
On the other hand, air separator 74 is located at (Fig. 3 and Fig. 4) between exsiccator 72 and ozonizer 73.This air separator 74 is to make airborne oxygen than oxygen permeable membrane 74a(Fig. 7 of the material of the easy infiltration of nitrogen by having) be housed in the outer cover 74d of tubular and form.Oxygen permeable membrane 74a is constituted as and can will by the dried pressurized air of exsiccator 72, be separated into oxygen-rich gas and the high nitrogen-rich gas of nitrogen gas concn that oxygen concentration is high.Particularly, oxygen permeable membrane 74a stops up hollow line 74b and form, and it is housed in outer cover 74d along its longitudinal direction, and wherein, hollow line 74b optionally makes the macromolecule of oxygen infiltration form by comparing with nitrogen, and its central authorities are formed with through hole 74c.In addition, the hollow line 74b that forms oxygen permeable membrane 74a, is preferably formed by the large vitreousness macromolecule of the degree of separation of oxygen and nitrogen, more preferably, degree of separation by oxygen and nitrogen is large especially, and the polyimide that mechanical strength, heat resistance and durability etc. are good forms.In addition, form the film of the hollow line 74b of oxygen permeable membrane 74a, can be at the uniform homogeneous membrane of film thickness direction upper density, or also can use the composite membrane forming unevenly in film thickness direction upper density because of many different hollow lines of intercalation internal diameter, external diameter and density, but preferably use because thering is the large anisotropic membrane of asymmetrical density structure seepage velocity on film thickness direction.More preferably, the thickness of hollow line 74b is set in the scope of 10 μ m～500 μ m, the external diameter of hollow line 74b is set in the scope of 50 μ m～2000 μ m.
For accommodating on the outer cover 74d upper surface of oxygen permeable membrane 74a, be formed with for a dry air introducing port 74e who is imported by the dried pressurized air of exsiccator 72, on the lower surface of outer cover 74d, be formed with the nitrogen-rich gas exhaust port 74f(Fig. 4 for the nitrogen-rich gas by after air separator 74 separation is discharged).Dry air introducing port 74e is connected in the upper end of each hollow line 74b of oxygen permeable membrane 74a, nitrogen-rich gas exhaust port 74f is connected in the lower end of each hollow line 74b of oxygen permeable membrane 74a, and dry air introducing port 74e and nitrogen-rich gas exhaust port 74f are connected with the through hole 74c of each hollow line 74b thus.In addition for accommodating the lower sidewall of the outer cover 74d of oxygen permeable membrane 74a, be formed with for discharging the oxygen-rich gas exhaust port 74g of oxygen-rich gas.It is constituted as the oxygen-rich gas that the film oxygen concentration of the hollow line 74b because of by oxygen permeable membrane 74a can be uprised and discharges from oxygen-rich gas exhaust port 74g.
Here, illustrate and utilize oxygen permeable membrane 74a by the high oxygen-rich gas nitrogen-rich gas separated principle high with nitrogen gas concn of oxygen concentration.Because dried pressurized air flows through after the through hole 74c of each hollow line 74b of oxygen permeable membrane 74a, thereby the film of hollow line 74b carries out the cause that thermal vibration forms the gap that supplied gas passes through, and the oxygen molecule in pressurized air, nitrogen molecular are ingested in above-mentioned gap.Now, due to the thickness of oxygen permeable membrane 74a be formed thinner, the speed of the film of oxygen molecule infiltration hollow line 74b is than the cause of fast about 2.5 times of the speed of the film of nitrogen molecular infiltration hollow line 74b, and oxygen molecule is promptly penetrated into the outer surface side of the hollow line 74b minute forcing down from the inner surface side of the film of the high hollow line 74b of dividing potential drop.Thus, the oxygen concentration of the outer surface side of the film of hollow line 74b uprises, the oxygen concentration step-down of the inner surface side of the film of hollow line 74b.Consequently, can utilize pressurized air to see through oxygen permeable membrane 74a and generate oxygen-rich gas, utilize and pressurized air is only passed through and through oxygen permeable membrane 74a, do not generate nitrogen-rich gas.In addition, the gap forming on the film of hollow line 74b because of above-mentioned thermal vibration is 5nm left and right.
On the other hand, the discharge opening of compressor 71 is connected in the air introducing port 72e of exsiccator 72 by the 1st supplying pipe 81, and the air outlet 72f of exsiccator 72 is connected in dry air introducing port 74e(Fig. 3～Fig. 5 of air separator 74 by the 2nd supplying pipe 82).In addition, the oxygen-rich gas exhaust port 74g of air separator 74 is connected in the oxygen-rich gas introducing port 73a of ozonizer 73 by the 3rd supplying pipe 83, is connected with one end of the 4th supplying pipe 84 on the ozone exhaust port 73b of ozonizer 73.In addition, the nitrogen-rich gas exhaust port 74f of air separator 74 is connected in the purge gas introducing port 72g of exsiccator 72 by scavenge pipe 76, is connected with one end of drainage pipe 77 on the purge gas discharge tube 72h of exsiccator 72.And the 1st supplying pipe 81 is provided with for storing by the compressed-air actuated gas tank 78 after compressor 71 compression, scavenge pipe 76 is provided with for adjusting the flow rate regulating valve 79 of the flow of the nitrogen-rich gas by this scavenge pipe 76.Above-mentioned gas tank 78 be set be for, even if the flow of oxygen-rich gas and nitrogen-rich gas is changed sharp, also can, to the pressurized air of supplying with sufficient amount in air separator 74, relax compressed-air actuated pressure oscillation simultaneously.In addition, the mark 86 of Fig. 3 and Fig. 4 is provided in a side of the one-way valve on the 4th supplying pipe 84.This one-way valve 86 is constituted as, and permission ozone gas below by the ozone nozzle 43 of describing, stops ozone gas to flow to ozonizer 73 from ozone nozzle 43 from ozonizer 73 flow directions.In addition, the mark 87 in Fig. 5 is that the mark 88 of Fig. 4 and Fig. 5 is for accommodating the basket of each member of ozone generating-device 70 in order to supply with the high-voltage power supply device of electric power to ozonizer 73.Also have, the mark the 89, the 89th in Fig. 4, for the fan of cooling ozonizer 73.
Turn back to Fig. 1, being more provided with casing 91 by the outlet pipe 16 of waste gas upstream side than ozone nozzle 43, in this casing 91, from waste gas upstream side, contain successively oxidation catalyst 92 and particulate filter 93.Oxidation catalyst 92 is integral catalyzers, and it applies the precious metal series catalysts such as platinum zeolite, platinum aluminium or platinum-palladium aluminium and forms on the honeycomb substrate of steinheilite system.Particularly, the oxidation catalyst 92 consisting of platinum zeolite is to be coated on honeycomb substrate and to form containing the paste that has carried out the zeolite powder after ion exchange with platinum.In addition the oxidation catalyst 92 consisting of platinum aluminium, is to be loaded with the γ-aluminium powder of platinum or the paste of θ-aluminium powder and to be coated on honeycomb substrate and to form containing.Also have, the oxidation catalyst 92 consisting of platinum-palladium aluminium is to be loaded with the γ-aluminium powder of platinum and palladium or the paste of θ-aluminium powder and to be coated on honeycomb substrate and to form containing.It is constituted as by above-mentioned oxidation catalyst 92 and makes NO in waste gas be oxidized to NO being more than or equal under the exhaust gas temperature of regulation 2.Here, the exhaust gas temperature of regulation, is the temperature of the regulation in the scope of 160～200 ℃, the preferred temperature of the regulation in the scope of 170～190 ℃, further preferably 180 ℃.Why allowing like this exhaust gas temperature of regulation have a scope, is that (NO is to NO because of active temperature 2oxidation starting temperature) difference according to being coated to the kind of the precious metal on the honeycomb substrate of oxidation catalyst 92.
Although do not illustrate, particulate filter 93 has the polygonal section being separated by the Porous next door of the pottery formation as steinheilite.This filter 93 is by utilizing packing component that adjacent entrance part and the export department of the many through holes that are parallel to each other that formed by these next doors are alternately encapsulated and are formed.In this filter 93, in the time of the next door of the waste gas of the motor 11 being imported into from the entrance part of filter 93 by Porous, the fine particle being contained in this waste gas can be discharged in the Hou Cong export department that is captured.
On the other hand, each of temperature transducer 51, turn-sensitive device 52 and load sensor 53 detects the control inputs that output is connected in controller 54, and the control output of controller 54 is connected to high-voltage power supply device 87, nitrogen-rich gas flow rate regulating valve 79, ozonizer 73, pump 27, hydrodynamic pressure adjustment valve 32 and open and close valve 33 for fluid.In controller 54, be provided with storage 56.In this storage 56, store in advance the having or not of action of the compressor 71 corresponding with the exhaust gas temperature of engine speed, engine loading, selective reduction type catalyzer 19 entrances, the having or not of the action of the having or not of the action of the aperture of nitrogen-rich gas flow rate regulating valve 79, the ozonizer 73 that driven by high-voltage power supply device 87, pump 27, aperture that hydrodynamic pressure is adjusted valve 32, the switching number of times in the unit time of open and close valve 33 for fluid.In addition NO and the NO the waste gas of discharging from motor 11 based on engine speed and engine loading variation, 2the variation of flow as mapping graph, be stored in storage 56 respectively.In addition, because the NO the waste gas of discharging from motor 11 is to NO 2flow-rate ratio because of the different cause of the kind of motor 11, above-mentioned mapping graph is according to every kind of motor 11 and changing.
The action of the waste gas cleaning plant once forming is like this described.After motor 11 has just started and during motor 11 light running, exhaust gas temperature is lower, 180 ℃ of less thaies.Here, why electing 180 ℃ of less thaies as, is because while being more than or equal to 180 ℃, even not to ozone supply gas in outlet pipe 16, oxidation catalyst 92 also can activate, and the NO in waste gas can be oxidized to NO by oxidized catalyzer 92 2.Therefore, the temperature of above-mentioned 180 ℃ is an example, in the occasion that has changed the kind of the precious metal on the honeycomb substrate that is coated in oxidation catalyst 92, need to change said temperature, this Temperature Setting is the temperature of the regulation in the scope of 160～200 ℃, is preferably set to the temperature of the regulation in the scope of 170～190 ℃.When temperature transducer 51, exhaust gas temperature to be detected lower, 180 ℃ of less thaies, when turn-sensitive device 52 and load sensor 53 detect the no-load running of motor 11 or light running, controller 54 each detection output drive compression machine 71 based on temperature transducer 51, turn-sensitive device 52 and load sensor 53, aperture with regulation is opened nitrogen-rich gas flow rate regulating valve 79, by high-voltage power supply device 87, make ozonizer 73 starts, while driven pump 27, with the aperture of regulation, open hydrodynamic pressure and adjust valve 32, fluid is opened and closed with open and close valve 33.After compressor 71 is driven, after air is compressed, be stored in gas tank 78.This pressurized air is removed water vapour (moisture) and is dried in exsiccator 72, and this dried pressurized air is separated into by air separator 74 oxygen-rich gas and the high nitrogen-rich gas of nitrogen gas concn that oxygen concentration is high.By the oxygen-rich gas after air separator 74 separation, be fed into ozonizer 73, a part for oxygen in oxygen-rich gas is changed into ozone by ozonizer 73, and this ozone gas is fed into ozone nozzle 43 after by the 4th supplying pipe 84 and ozone supply pipe 44.On the other hand, by the nitrogen-rich gas after air separator 74 separation, be fed into exsiccator 72 after by scavenge pipe 76, from drainage pipe 77, discharge together with the water vapour (moisture) after separated with the device 72 that is dried.Like this, because exsiccator 72 does not use, there is the needed oxygen-rich gas of ozone, and use the unwanted nitrogen-rich gas of generation ozone to be regenerated, so can make exsiccator 72 effectively regenerate.In addition, owing to can the air by after compressor 71 compressions not being directly used in and making exsiccator 72 regeneration, so can suppress the consumption figure by the air after compressor 71 compressions.Consequently, can reduce compressor 71 capacity that spues, so can seek the miniaturization of compressor 71.
In addition, if oxygen-rich gas is increased, steam vapour amount (amount of moisture) in the pressurized air that the device 72 that is dried is removed also increases, even so, but owing to will strengthening the cause of the aperture of nitrogen-rich gas flow rate regulating valve 79 in this occasion, nitrogen-rich gas by air separator 74 separation also increases, so can utilize the nitrogen-rich gas of this increase that the water vapour of the increase in exsiccator 72 (moisture) is removed.Consequently, even if oxygen-rich gas has increase and decrease, nitrogen-rich gas also increases and decreases with this increase and decrease, therefore, can make exsiccator 72 effectively regenerate.In addition, because can use adjusted the voltage stabilizer of use by the compressed-air actuated pressure after compressor 71 compressions, so can form ozone generating-device 70 with fewer component, can reduce compressed-air actuated stream impedance, so can make the further miniaturization of compressor 71.In addition,, even be there is hydrocarbon in the pressurized air after compressor 71 compressions, this hydrocarbon adheres to or is non-cohesive on oxygen permeable membrane 74a, can it be positively separated into oxygen-rich gas and nitrogen-rich gas by oxygen permeable membrane 74a.Consequently, it is upper no matter whether hydrocarbon is attached to oxygen permeable membrane 74a, and the oxygen-rich gas being undertaken by oxygen permeable membrane 74a and the separating property of nitrogen-rich gas can not reduce.
On the other hand, the ozone gas that is supplied to ozone nozzle 43 is sprayed (supply) to outlet pipe 16 from ozone nozzle 43.Here,, to ozone supply gas in outlet pipe 16, be why in order to utilize ozone gas to make a part of the NO in waste gas change into reactive high NO 2, make to be directed to NO in the waste gas in selective reduction type catalyzer 19 to NO 2flow-rate ratio approach NO and the NO that the Urea Series fluid 22 in selective reduction type catalyzer 19 carries out 2to N 2the reduction reaction ratio 1 to 1 of carrying out the soonest.So the mapping graph of controller 54 based on being stored in storage 56, obtains NO the waste gas of discharging from motor 11 to NO 2flow-rate ratio, set to the supply flow of the outlet pipe 16 of above-mentioned ozone gas, to make to be directed to NO in selective reduction type catalyzer 19 to NO 2flow-rate ratio approach 1 to 1.As shown in the formula of the 1st mode of execution (1), above-mentioned ozone gas is fed into after outlet pipe 16, by ozone (O 3) part of the NO in waste gas is promptly changed into NO 2.
On the other hand, when pump 27 is driven, hydrodynamic pressure adjust valve 32 with the aperture of regulation be opened, after fluid opened and closed with open and close valve 33, Urea Series fluid 22 is sprayed (supply) in outlet pipe 16 off and on by fluid supply line 24 is rear.Here, why in outlet pipe 16, supplying with Urea Series fluid 22, is in order to make it as by the NO in waste gas x(NO and NO 2) be reduced into N 2reducing agent and play a role.NO and NO when being contained in the waste gas of discharging from motor 11 2, the NO in this waste gas the NO of a part after by ozone oxidation 2, after Urea Series fluid 22 is directed in selective reduction type catalyzer 19, even when 180 ℃ of lower less thaies of exhaust gas temperature, reactive high NO 2also can in selective reduction type catalyzer 19, carry out selective reduction and be reduced into N with Urea Series fluid 22 2.When consequently, exhaust gas temperature is lower, also can effectively reduce NO x.In addition, when 180 ℃ of lower less thaies of exhaust gas temperature, oxidation catalyst 92 can activate, can not bring into play NO is oxidized to NO 2effect.
Concrete chemical reaction in selective reduction type catalyzer 19, the occasion that is aqueous solution of urea at Urea Series fluid 22, represents that by formula (2) and the formula (3) of the 1st mode of execution the occasion that is ammonia at Urea Series fluid 22 represents by the formula (4) of the 1st mode of execution.
In addition,, when exhaust gas temperature is more than or equal to 180 ℃, the detection of controller 54 based on temperature transducer 51 exported and compressor 71 and ozonizer 73 stopped, and closes nitrogen-rich gas flow rate regulating valve 79 simultaneously.This be because, in exhaust gas temperature, become after higher high temperature, oxidation catalyst 92 is activate, thereby performance NO is oxidized to NO 2the cause of effect.That is, in exhaust gas temperature, become and be more than or equal to after 180 ℃, oxidation catalyst 92 is just oxidized to the NO in waste gas reactive high NO 2so, the NO that this reactivity is high 2just from the fluid tip 23 of fluid supply part 21, flow in selective reduction type catalyzer 19 with together with Urea Series fluid 22 being fed into outlet pipe 16.Consequently, even if exhaust gas temperature uprises, reactive high NO 2also can in selective reduction type catalyzer 19, carry out selective reduction and be reduced into N with Urea Series fluid 22 2so, even if exhaust gas temperature uprises, also can effectively reduce NO x.Therefore, can almost in whole exhaust gas temperature region, effectively reduce NO x.
In addition, in the above-mentioned the 1st and the 2nd mode of execution, waste gas cleaning plant of the present invention is used in diesel engine, but also waste gas cleaning plant of the present invention can be used on petrol engine.In addition, in the above-mentioned the 1st and the 2nd mode of execution, waste gas cleaning plant of the present invention is used in the diesel engine with turbocharger, but also waste gas cleaning plant of the present invention can be used on naturally aspirated diesel engine or naturally aspirated petrol engine.In addition, in the above-mentioned the 1st and the 2nd mode of execution, ozone nozzle has been located at than fluid tip and has more leaned in the outlet pipe of waste gas upstream side, but also ozone nozzle can be located at than fluid tip more by the outlet pipe of exhaust gas downstream side.In addition, in the above-mentioned the 1st and the 2nd mode of execution, as ozonizer, used the ozonizer of silent discharge type, but as ozonizer also can use creeping discharge formula (Japanese: put Electricity type along face), to air radiation ultraviolet ray, there is ozone type, brine electrolysis and occur ozone type etc. the ozonizer of this mode.Also have, in above-mentioned the 2nd mode of execution, between compressor and exsiccator, be provided with gas tank, but at the flow of oxygen-rich gas and nitrogen-rich gas, occasion jumpy does not occur, also can not establish gas tank.
Embodiment
Below embodiments of the invention are elaborated together with comparative example.
(embodiment 1)
On the outlet pipe 16 of the diesel engine 11 of the array that is 8000cc in air displacement as shown in Figure 1,6 cylinder band turbochargers, be provided with selective reduction type catalyzer 19.In addition, more leaning in the outlet pipe 16 of waste gas upstream side than selective reduction type catalyzer 19, be provided with for supplying with the fluid tip 23 of aqueous solution of urea 22.Here, selective reduction type catalyzer 19 is to be coated in by containing the paste that has carried out the zeolite powder after ion exchange with copper the Cu-series catalyst being made on honeycomb substrate.In addition, than fluid tip 23, more by the outlet pipe 16 of waste gas upstream side, be provided with the ozone nozzle 43 for ozone supply 42.Here, the aqueous solution of urea 22 of atomized spray will be from fluid tip 23, spray (supply) and be equivalent to the amount with ammonia conversion (reaction of aqueous solution of urea 22 based on above-mentioned formula (2) is hydrolyzed into the amount of ammonia) supply 200ppm, select the emitted dose (delivery volume) of the ozone 42 spraying from ozone nozzle 43 as 30ppm as.Using this waste gas cleaning plant as embodiment 1.
(embodiment 2)
Except selecting the emitted dose (delivery volume) of the ozone from ozone nozzle ejection as 55ppm as, formed the waste gas cleaning plant identical with embodiment 1.Using this waste gas cleaning plant as embodiment 2.
(embodiment 3)
Except forming to spray the mode of ammonia from fluid tip, the emitted dose (delivery volume) of the ammonia from this fluid tip injection is elected as beyond 200ppm, formed the waste gas cleaning plant identical with embodiment 1.Using this waste gas cleaning plant as embodiment 3.
(embodiment 4)
Except selecting the emitted dose (delivery volume) of the ozone from ozone nozzle ejection as 55ppm as, formed the waste gas cleaning plant identical with embodiment 3.Using this waste gas cleaning plant as embodiment 4.
(comparative example 1)
Except not from ozone nozzle ejection ozone, formed the waste gas cleaning plant identical with embodiment 1.This waste gas cleaning plant as a comparative example 1.
(comparative example 2)
Except not from ozone nozzle ejection ozone, formed the waste gas cleaning plant identical with embodiment 3.This waste gas cleaning plant as a comparative example 2.
(comparative test 1 and evaluation)
Make rotating speed and the load variations of motor, measured respectively the NO while making the exhaust gas temperature of discharging from waste pipe of embodiment 1～4 and comparative example 1 and 2 gradually rise to 200 ℃ from 100 ℃ xslip.The results are shown in Fig. 8 and Fig. 9.
As can be seen from Figure 8, NO when 100 ℃ and 200 ℃ in the waste gas cleaning plant of comparative example 1 xslip is respectively about 3% and about 60%, to this, and NO when 100 ℃ of embodiment 1 waste gas cleaning plantes and 200 ℃ xslip uprises, and is respectively about 17% and about 70%, NO when 100 ℃ of embodiment 2 waste gas cleaning plantes and 200 ℃ xit is higher that slip becomes, and is respectively about 30% and about 80%.That is, than the waste gas cleaning plant that there is no the comparative example 1 of ozone supply, supplied with this side of waste gas cleaning plant of the embodiment 1 of 30ppm ozone, within the scope of the exhaust gas temperature of 100～200 ℃, NO xslip has improved, and than the waste gas cleaning plant of having supplied with the embodiment 1 of 30ppm ozone, has supplied with this side of waste gas cleaning plant of the embodiment 2 of 55ppm ozone, within the scope of the exhaust gas temperature of 100～200 ℃, and NO xslip has improved.This can be considered to, due to the NO and the NO that are directed in selective reduction catalyzer 2flow-rate ratio, than comparative example, 1 embodiment 1 is more approaching to N 2reduction reaction carry out rapidly 1 to 1, than embodiment 1 embodiment 2, especially more approach to N 2reduction reaction carry out rapidly 1 to 1.
As can be seen from Figure 9, NO when 100 ℃ and 200 ℃ in the waste gas cleaning plant of comparative example 2 xslip is respectively about 4% and about 70%, to this, and the NO in embodiment 3 waste gas cleaning plant when 100 ℃ and 200 ℃ xslip uprises, and is respectively about 33% and about 86%, the NO in embodiment 4 waste gas cleaning plant when 100 ℃ and 200 ℃ xit is higher that slip becomes, and is respectively about 60% and about 99%.That is, obtain cicada than the waste gas cleaning plant that there is no the comparative example 2 of ozone supply, supplied with this side of waste gas cleaning plant of the embodiment 3 of 30ppm ozone, within the scope of the exhaust gas temperature of 100～200 ℃, NO xslip has improved, and than the waste gas cleaning plant that has sprayed the embodiment 3 of 30ppm ozone, has supplied with this side of waste gas cleaning plant of the embodiment 4 of 55ppm ozone, within the scope of the exhaust gas temperature of 100～200 ℃, and NO xslip has improved.This can be considered to due to the NO and the NO that are directed in selective reduction catalyzer 2flow-rate ratio, than comparative example, 2 embodiment 3 these sides will approach to N 2reduction reaction carry out rapidly 1 to 1, more approaching to N than embodiment 3 embodiment 4 these sides 2reduction reaction 1 to 1 the cause of carrying out rapidly.
From Fig. 8 and Fig. 9, than supplied with the waste gas cleaning plant of embodiment 1, embodiment 2 and the comparative example 1 of aqueous solution of urea in selective reduction type catalyzer, to this side of waste gas cleaning plant who has supplied with embodiment 3, embodiment 4 and the comparative example 2 of ammonia in selective reduction type catalyzer, within the scope of the exhaust gas temperature of 100～200 ℃, NO xslip has improved respectively.This can be considered to, due to than supply with aqueous solution of urea in selective reduction type catalyzer, in selective reduction type catalyzer, supply with ammonia this side, NO and NO 2to N 2the reduction reaction cause of carrying out rapidly.
(embodiment 5)
In the outlet pipe 16 of the diesel engine 11 with turbocharger 17 of array 6 cylinders that are 8000cc in air displacement as shown in Figure 2,, be provided with selective reduction type catalyzer 19.In addition than selective reduction type catalyzer 19, more by the outlet pipe 16 of waste gas upstream side, be provided with for supplying with the fluid tip 23 of aqueous solution of urea.Here, selective reduction type catalyzer 19 is to be coated in by containing the paste that has carried out the zeolite powder after ion exchange with copper the Cu-series catalyst of making on honeycomb substrate.In addition, than fluid tip 23, more by the outlet pipe 16 of waste gas upstream side, be provided with the ozone nozzle 43 for ozone supply gas.In addition, the top of ozone supply pipe 44 has been connected on ozone nozzle 43, the cardinal extremity of ozone supply pipe 44 has been connected on the 4th supplying pipe 84 of ozone generating-device 70.As shown in Fig. 3～Fig. 5, this ozone generating-device 70 has compressor 71, gas tank 78, exsiccator 72, air separator 74, ozonizer 73, flow rate regulating valve 79, one-way valve 86, high-voltage power supply device 87.Compressor 71 drives by the storage battery of VDC 24V.As exsiccator 72, used industrial society of space portion (Japanese: " the UBE diaphragm type exsiccator (Japanese: メ Application Block レ Application De ラ イ ヤ ー) " Yu BuXingchan society) manufactured, as air separator 74, " the UBEN that has used industrial society of space portion to manufacture 2separator ".Here, the aqueous solution of urea of atomized spray will be from fluid tip 23, spray (supply) and be equivalent to supply with 200ppm amount with ammonia conversion (reaction of aqueous solution of urea based on above-mentioned formula (2) is hydrolyzed into the amount of ammonia), select the emitted dose (delivery volume) of the ozone gas spraying from ozone nozzle 43 as 30ppm as.But also more leaning in the outlet pipe 16 of waste gas upstream side than fluid tip 23 and ozone nozzle 43, from waste gas upstream side, oxidation catalyst 92 and particulate filter 93 have been set gradually.Here, oxidation catalyst 92 has been used and will contain the paste that has carried out the aluminium powder after ion exchange with platinum and be coated in the catalyzer of the platinum system making on honeycomb substrate.Using this waste gas cleaning plant as embodiment 5.
(embodiment 6)
Except selecting the emitted dose (delivery volume) of the ozone from ozone nozzle ejection as 55ppm as, formed the waste gas cleaning plant identical with embodiment 5.Using this waste gas cleaning plant as embodiment 6.
(embodiment 7)
Except forming to spray the mode of ammonia from fluid tip, the emitted dose (delivery volume) of the ammonia from this fluid tip injection is elected as beyond 200ppm, formed the waste gas cleaning plant identical with embodiment 5.Using this waste gas cleaning plant as embodiment 7.
(embodiment 8)
Except selecting the emitted dose (delivery volume) of the ozone from ozone nozzle ejection as 55ppm as, formed the waste gas cleaning plant identical with embodiment 7.Using this waste gas cleaning plant as embodiment 8.
(comparative example 3)
Except not from ozone nozzle ejection ozone, formed the waste gas cleaning plant identical with embodiment 5.This waste gas cleaning plant as a comparative example 3.
(comparative example 4)
Except not from ozone nozzle ejection ozone, formed the waste gas cleaning plant identical with embodiment 7.This waste gas cleaning plant as a comparative example 4.
(comparative test 2 and evaluation)
Make rotating speed and the load variations of motor, the NO when having measured respectively the exhaust gas temperature that makes to discharge from the waste pipe of embodiment 5～8 and comparative example 3 and 4 and gradually rising to 200 ℃ from 150 ℃ xslip.The results are shown in Figure 10 and Figure 11.
As can be seen from Figure 10, in the waste gas cleaning plant of comparative example 3, NO when 150 ℃ of exhaust gas temperature and 170 ℃ xslip is respectively about 36% and about 59%, to this, and in embodiment 5 waste gas cleaning plant, NO when 150 ℃ of exhaust gas temperature and 170 ℃ xslip uprises, and is respectively about 51% and about 66%, in embodiment 6 waste gas cleaning plant, and NO when 150 ℃ of exhaust gas temperature and 170 ℃ xit is higher that slip becomes, and is respectively about 66% and about 73%.That is, than the waste gas cleaning plant that there is no the comparative example 3 of ozone supply, supplied with this side of waste gas cleaning plant of the embodiment 5 of 30ppm ozone, within the scope of the exhaust gas temperature of 150～170 ℃, NO xslip has improved, and than the waste gas cleaning plant of having supplied with the embodiment 5 of 30ppm ozone, has supplied with this side of waste gas cleaning plant of the embodiment 6 of 55ppm ozone, within the scope of the exhaust gas temperature of 150～170 ℃, and NO xslip has improved.This can be considered to due to the NO and the NO that are directed in selective reduction catalyzer 2flow-rate ratio, than comparative example, 3 embodiment 5 these sides will approach to N 2reduction reaction carry out rapidly 1 to 1, more approaching to N than embodiment 5 embodiment 6 these sides 2reduction reaction 1 to 1 the cause of carrying out rapidly.In addition, in comparative example 3, embodiment 5 and embodiment's 6 waste gas cleaning plant, NO when exhaust gas temperature is more than or equal to 180 ℃ xit is almost identical that slip becomes.This can be considered to because exhaust gas temperature becomes while being more than or equal to 180 ℃, oxidation catalyst activity and brought into play the NO in waste gas is oxidized to NO 2the cause of effect.
As can be seen from Figure 11, in the waste gas cleaning plant of comparative example 4, NO when 150 ℃ of exhaust gas temperature and 170 ℃ xslip is respectively about 49% and about 78%, to this, and in embodiment 7 waste gas cleaning plant, NO when 150 ℃ of exhaust gas temperature and 170 ℃ xslip uprises, and is respectively about 73% and about 89%, in embodiment 8 waste gas cleaning plant, and NO when 150 ℃ of exhaust gas temperature and 170 ℃ xit is higher that slip becomes, and is respectively about 98% and about 99%.That is, than the waste gas cleaning plant that there is no the comparative example 4 of ozone supply, supplied with this side of waste gas cleaning plant of the embodiment 7 of 30ppm ozone, within the scope of the exhaust gas temperature of 150～170 ℃, NO xslip has improved, and than the waste gas cleaning plant that has sprayed the embodiment 7 of 30ppm ozone, has supplied with this side of waste gas cleaning plant of the embodiment 8 of 55ppm ozone, within the scope of the exhaust gas temperature of 150～170 ℃, and NO xslip has improved.This can be considered to, and is directed to NO and NO in selective reduction catalyzer 2flow-rate ratio, than comparative example, 4 embodiment 7 these sides will approach to N 2reduction reaction carry out rapidly 1 to 1, more approaching to N than embodiment 7 embodiment 8 these sides 2reduction reaction 1 to 1 the cause of carrying out rapidly.In addition, in comparative example 4, embodiment 7 and embodiment's 8 waste gas cleaning plant, NO when exhaust gas temperature is more than or equal to 180 ℃ xit is almost identical that slip becomes.This can be considered to become while being more than or equal to 180 ℃ when exhaust gas temperature, oxidation catalyst activity and brought into play the NO in waste gas is oxidized to NO 2the cause of effect.
From Figure 10 and Figure 11, than supplied with the waste gas cleaning plant of embodiment 5, embodiment 6 and the comparative example 3 of aqueous solution of urea in selective reduction type catalyzer, to this side of waste gas cleaning plant who has supplied with embodiment 7, embodiment 8 and the comparative example 4 of ammonia in selective reduction type catalyzer, within the scope of the exhaust gas temperature of 150～200 ℃, NO xslip has improved respectively.This can be considered to, than supply with aqueous solution of urea in selective reduction type catalyzer, in selective reduction type catalyzer, supply with ammonia this side, NO and NO 2to N 2the reduction reaction cause of carrying out rapidly.
Industrial utilizability
Air purifying apparatus of the present invention can be as contained NO in the waste gas of the motors such as minimizing diesel engine xthereby the device of purifying exhaust air is used.
Description of reference numerals
11 diesel engine (motor)
16 outlet pipes
19 selective reduction type catalyzer
21 fluid supply parts
22 Urea Series fluids
23 fluid tips
41,61 ozone supply parts
42 ozone
43 ozone nozzles
70 ozone generating-devices
71 compressors
72 exsiccators
73 ozonizers
74 air separators
74a oxygen permeable membrane
76 scavenge pipes
78 gas tanks
79 nitrogen-rich gas flow rate regulating valves
92 oxidation catalysts
93 particulate filters

Claims (9)

1. a waste gas cleaning plant, is characterized in that, has:
Selective reduction type catalyzer (19), this selective reduction type catalyzer (19) is located in the outlet pipe (16) of motor (11), can be by the NO in waste gas xbe reduced into N 2;
Fluid supply part (21), this fluid supply part (21) has fluid tip (23), this fluid tip (23) is facing to more leaning on the outlet pipe (16) of waste gas upstream side than described selective reduction type catalyzer (19), this fluid supply part (21) is supplied with Urea Series fluid (22) from this fluid tip (23) to described outlet pipe (16), and this Urea Series fluid (22) plays a role as reducing agent in described selective reduction type catalyzer (19); With
Ozone supply parts (41), these ozone supply parts (41) have ozone nozzle (43), this ozone nozzle (43) facing to than described selective reduction type catalyzer (19) more by waste gas upstream side and than described fluid tip (23) more by the outlet pipe (16) of waste gas upstream side or exhaust gas downstream side, these ozone supply parts (41) from this ozone nozzle (43) to described outlet pipe (16) supply the NO in described waste gas can be oxidized to NO 2ozone (42).
2. the waste gas cleaning plant of recording as claim 1, is characterized in that also having: ozone generating-device (70) and oxidation catalyst (92), and with airborne oxygen, there is described ozone (42) in this ozone generating-device (70); This oxidation catalyst (92) is arranged on than described fluid tip (23) and described ozone nozzle (42) and more leans in the outlet pipe (16) of waste gas upstream side, can the NO in described waste gas be oxidized to NO in the exhaust gas temperature that is more than or equal to regulation 2.
3. the waste gas cleaning plant of recording as claim 2, is characterized in that, described ozone generating-device (70) has: compressor (71), and this compressor (71) is for pressurized air; Exsiccator (72), this exsiccator (72) is for making by the Compressed air drying after this compressor (71) compression; Ozonizer (73), this ozonizer (73) is for changing into ozone a part for the oxygen by the dried pressurized air of this exsiccator (72); And air separator (74), this air separator (74) is arranged between described exsiccator (72) and described ozonizer (73), be used for being separated into by the dried pressurized air of described exsiccator (72) oxygen-rich gas and the high nitrogen-rich gas of nitrogen gas concn that oxygen concentration is high
This ozone generating-device (70) is constituted as, after being imported in described ozonizer (73), a part for oxygen by the oxygen-rich gas of described air separator (74) separation changes into ozone by described ozonizer (73), by being removed the moisture in described exsiccator (72) and make described exsiccator (72) regeneration by the separated nitrogen-rich gas of described air separator (74).
4. the waste gas cleaning plant of recording as claim 3, it is characterized in that, described air separator (74) consists of oxygen permeable membrane (74a), described oxygen-rich gas generates by making to be seen through described oxygen permeable membrane (74a) by the dried pressurized air of described exsiccator (72), and described nitrogen-rich gas does not see through described oxygen permeable membrane (74a) by making only to be passed through by the dried pressurized air of described exsiccator (72) and generates.
5. as claim 3 or 4 waste gas cleaning plantes of recording, it is characterized in that, be constituted as, by the nitrogen-rich gas after described air separator (74) separation, by scavenge pipe (76), be fed into described exsiccator (72), on described scavenge pipe (76), be provided with nitrogen-rich gas flow rate regulating valve (79), this nitrogen-rich gas flow rate regulating valve (79) is for adjusting by the flow of the described nitrogen-rich gas of this scavenge pipe (76).
6. the waste gas cleaning plant of recording as any one in claim 3 to 5, it is characterized in that, between described compressor (71) and described exsiccator (72), be provided with gas tank (78), this gas tank (78) is for storing by the pressurized air after described compressor (71) compression.
7. as claim 1 or 2 waste gas cleaning plantes of recording, it is characterized in that, described Urea Series fluid (22) is any one in ammonia or aqueous solution of urea.
8. the waste gas cleaning plantes of recording as claim 1 or 2, is characterized in that, described selective reduction type catalyzer (19) applies zeolite or zirconium oxide and forms on honeycomb substrate.
9. the waste gas cleaning plant of recording as claim 2, it is characterized in that, more more leaning on the outlet pipe (16) of exhaust gas downstream side upper by waste gas upstream side and than described oxidation catalyst (92) than described fluid tip (23) and described ozone nozzle (43), be provided with for catching the atomic particulate filter (93) of described waste gas.
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WO2012124531A1 (en) 2012-09-20
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